As well known to those skilled in the art, it is possible to remove water from mixtures thereof with organic liquids by various techniques including adsorption or distillation. These conventional processes, particularly distillation, are however, characterized by high capital cost. In the case of distillation for example the process requires expensive distillation towers, heaters, heat exchangers (reboilers, condensers, etc.), together with a substantial amount of auxiliary equipment typified by pumps, collection vessels, vacuum generating equipment, etc.
Such operations are characterized by high operating costs principally costs of heating and cooling - plus pumping, etc.
Furthermore the properties of the materials being separated, as is evidenced by the distillation curves, may be such that a large number of plates may be required, etc. When the material forms an azeotrope with water, additional problems may be present which for example, would require that separation be effected in a series of steps (e.g. as in two towers) or by addition of extraneous materials to the system.
There are also comparable problems which are unique to adsorption systems.
It has been found to be possible to utilize membrane systems to separate mixtures of miscible liquids by pervaporation. In this process, the charge liquid is brought into contact with a membrane film; and one component of the charge liquid preferentially permeates the membrane. The permeate is then removed as a vapor from the downstream side of the film--typically by sweeping with a carrier gas or by reducing the pressure below the saturated vapor pressure of the permeating species.
Illustrative membranes which have been employed in prior art techniques include those set forth in the following table:
TABLE ______________________________________ Separating Layer References ______________________________________ Nafion brand of Cabasso and Liu perfluorosulfonic acid J. Memb. Sci. 24, 101 (1985) Sulfonated polyethylene Cabasso, Korngold & Liu J. Pol. Sc: Letters, 23, 57 (1985) Fluorinated polyether USP 4,526,948 or Carboxylic Acid fluorides to Dupont as assignee of Resnickto Selemion AMV Wentzlaff brand of Asahi Glass Boddeker & Hattanbach cross-linked styrene J. Memb. Sci. 22,333 butadiene (with quaternary (1985) ammonium residues on a polyvinyl chloride backing) Cellulose triacetate Wentzlaff, Boddeker & Hattanback, J. Memb. Sci. 22, 333 (1985) Polyacrylonitrile Neel, Aptel & Clement Desalination 53, 297 (1985) Crosslinked Eur. Patent 0 096 Polyvinyl Alcohol 339 to GFT as assignee of Bruschke Poly(maleimide- Yoshikawa et al acrylonitrile) J. Pol. Sci. 22, 2159 (1984) Dextrine - Chem. Econ. Eng. isophorone diisocyanate Rev., 17, 34 (1985) ______________________________________
The cost effectiveness of a membrane is determined by the selectivity and productivity. Of the membranes commercially available, an illustrative polyvinyl alcohol membrane of high performance is that disclosed in European patent 0 096 339 A2 of GFT as assignee of Bruschke--published Dec. 21, 1983.
European Patent 0 096 339 A2 to GFT as assignee of Bruschke discloses, as cross-linking agents, diacids (typified by maleic acid or fumaric acid); dihalogen compounds (typified by dichloroacetone or 1,3-dichloroisopropanol); aldehydes, including dialdehydes, typified by formaldehyde. These membranes are said to be particularly effective for dehydration of aqueous solutions of ethanol or isopropanol.
This reference discloses separation of water from alcohols, ethers, ketones, aldehydes, or acids by use of composite membranes. Specifically the composite includes (i) a backing typically about 120 microns in thickness, on which is positioned (ii) a microporous support layer of a polysulfone or a polyacrylonitrile of about 50 microns thickness, on which is positioned (iii) a separating layer of cross-linked polyvinyl alcohol about 2 microns in thickness.
Polyvinyl alcohol may be cross-linked by use of difunctional agents which react with the hydroxyl group of the polyvinyl alcohol. Typical cross-linking agent may include dialdehydes (which yield acetal linkages), diacids or diacid halides (which yield ester linkages), dihalogen compounds or epichlorhydrin (which yield ether linkages) olefinic aldehydes (which yield ether/acetal linkages), boric acid (which yields boric ester linkages), sulfonamidoaldehydes, etc.
U.S. Pat. No. 4,728,429 to Cabasso et al, U.S. Pat. No. 4,067,805 to Chiang et al, U.S. Pat. No. 4,526,948 to Resnick, U.S. Pat. No. 3,750,735 to Chiang et al, and U.S. Pat. No. 4,690,766 to Linder et al provide additional background.
Additional prior art which may be of interest includes:
Mobility of Spin Probes in Quaternized Poly(4-Vinvlpvridine) Membranes, Makino, Hamada, and Iijima, in Polym. J. (Toyko), 19(6), 737-45, 1987.
Effect of Quaternization on the Pervaporation Rate of Water Through Poly(4-Vinylpyridine) Membrane, Hamaya, and Yamada, in Kobunshi Ronbunshu, 34(7), 545-7, 1977.
Preparation of Separation Membranes, Yamamoto, Toi, and Mishima, patent #JP 61/161109 A2, Jul 21 1986. (Japanese).
Separation of Some Aqueous Amine Solutions by Pervaporation through Poly(4-Vinylpyridine) Membrane Yamada and Hamaya, in Kobunshi Ronbunshu, 39(6), 407-14, 1982.
Complex Formation of Crosslinked Poly(4-Vinylpyridine) Resins with Copper(II), by Nishide, Deguchi, and Tsuchida, in Bulletin of the Chemical Society of Japan, Vol. 49(12), 3498-3501 (1976).
It is an object of this invention to provide a novel process for separation of water from organic oxygenates such as isopropyl alcohol. Other objects will be apparent to those skilled in the art.